CN110323415A - The manufacturing method of lithium secondary battery and the lithium secondary battery - Google Patents

The manufacturing method of lithium secondary battery and the lithium secondary battery Download PDF

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Publication number
CN110323415A
CN110323415A CN201810836005.6A CN201810836005A CN110323415A CN 110323415 A CN110323415 A CN 110323415A CN 201810836005 A CN201810836005 A CN 201810836005A CN 110323415 A CN110323415 A CN 110323415A
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China
Prior art keywords
binder
secondary battery
lithium secondary
cathode
electrode active
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CN201810836005.6A
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CN110323415B (en
Inventor
吴承旼
吕悦梅
高琦锡
李尹圣
金兌炫
文晙荣
高乐奎
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Modern Auto Co Ltd
Industry Academic Cooperation Foundation of INU
Kia Corp
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Modern Auto Co Ltd
Kia Motors Corp
Industry Academic Cooperation Foundation of INU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0459—Cells or batteries with folded separator between plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
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    • H01M4/00—Electrodes
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention discloses a kind of lithium secondary battery, which can be by improving output characteristics, life characteristic and electrode adhesion stability in the cathode comprising silicon using the binder comprising heparin or Lithium polyacrylate (LiPAA).According to the one side of the disclosure, lithium secondary battery includes: anode；Cathode；Diaphragm is arranged between positive electrode and negative electrode；And electrolyte, wherein cathode includes electrode active material, binder and conductive material comprising silica-base material and graphite, and binder includes any one of heparin and Lithium polyacrylate (LiPAA).

Description

The manufacturing method of lithium secondary battery and the lithium secondary battery
Technical field
This disclosure relates to a kind of lithium secondary battery.
Background technique
In general, the lithium secondary battery including electroactive material has high work electricity compared with lead battery or nickel/cadmium cell Pressure and high energy density.Therefore, lithium secondary battery is widely used as the energy of electric vehicle (EV) and hybrid electric vehicle (HEV) Measure storage device.
The mileage of electric vehicle can be improved by increasing battery energy density.In order to increase battery energy density, answer The energy density of material used in the raising battery.Recently, have been developed that using Ni base, Co base or Mn base anode material and The lithium secondary battery of graphite (graphite) cathode.
However, the limitation in order to overcome energy density, is also researching and developing the other materials that can substitute these materials.Mesh Before, the research to silicon is energetically being carried out, with graphite-phase ratio, silicon is with the large capacity and high energy for being more than 4000mAh/g Density.
Summary of the invention
The one side of the disclosure provides a kind of lithium secondary battery, which can be by the cathode comprising silicon Output characteristics, life characteristic and electrode are improved using the binder comprising heparin (Heparin) or Lithium polyacrylate (LiPAA) Adhesion stability.
The other aspects of the disclosure will be set forth in part in the description which follows, and partly will be bright from the description It is aobvious, or can be by the practice of the disclosure come acquistion.
According to the one side of the disclosure, a kind of lithium secondary battery includes: anode；Cathode；Diaphragm is arranged in positive electrode and negative electrode Between；And electrolyte, wherein cathode includes electrode active material, binder and conduction material comprising silica-base material and graphite Material, and binder includes any one of heparin and Lithium polyacrylate (LiPAA).
The partial size of silica-base material can be for 50nm or bigger and less than 10 μm.
The amount for the binder that cathode includes greatly and can be less than 50wt% for 1wt% or more.
Conductive material may include at least one of carbon black and gas-phase growth of carbon fibre (VGCF).
Cathode can include conductive material and binder with the ratio of 1:1 to 1:10.
Binder may further include dopamine (Dopamine) polymerization heparin.
According to another aspect of the present disclosure, a kind of manufacturing method of lithium secondary battery includes: using ball-milling device to including The electrode active material and binder of silica-base material carry out the first grinding；Conductive material is added to through the first grinding acquisition The compound of electrode active material and binder, and the second grinding is carried out to compound using ball-milling device；And to passing through the The compound of electrode active material, binder and conductive material that two grindings obtain is heat-treated.
Carrying out the first grinding may include: that electrode active material and binder are put into ball-milling device；It will be with 20:1 (wt%) ZrO of ratio mixing2The compound of ball and powder is put into ball-milling device；And it is repeated 3 times following procedure: with The speed of 500rpm carries out grinding 1 hour, rests 30 minutes.
Carrying out heat treatment may include: to carry out heat treatment 1 hour at 300 DEG C in argon (Ar) gas.
Conductive material may include at least one of carbon black and gas-phase growth of carbon fibre (VGCF).
Binder may include any one of heparin, Lithium polyacrylate (LiPAA) and dopamine polymerization heparin.
Detailed description of the invention
According to the specific embodiment below in conjunction with attached drawing, the these and/or other aspects of the disclosure will become aobvious and easy See and be easier to understand, in which:
Fig. 1 conceptually illustrates lithium secondary battery according to the exemplary embodiment of the disclosure.
Fig. 2 shows cathode according to the exemplary embodiment of the disclosure.
Fig. 3 A and Fig. 3 B conceptually illustrate the charge/discharge variation of cathode according to the exemplary embodiment of the disclosure.
Fig. 4 shows the cycle performance figure of cathode according to the exemplary embodiment of the disclosure.
Fig. 5 shows the discharge cycle performance of cathode according to the exemplary embodiment of the disclosure.
Specific embodiment
Throughout the specification, identical appended drawing reference refers to identical element.This specification does not describe the institute of embodiment There is component, and the general information in disclosure technical field or the overlay information between embodiment will not described.
It will be appreciated that using the terms "include", "comprise", " it includes " and/or when " it includes ", table in this specification Show the presence of the component, but is not excluded for the presence or addition of one or more of the other component.
It will be appreciated that singular "an", "one" and "the" include plural form, unless context understands earth's surface It is shown as opposite.
Hereinafter, embodiment of the disclosure is described in detail with table with reference to the accompanying drawings.Firstly, it is secondary to describe lithium Then battery will describe binder according to the embodiment.
Fig. 1 conceptually illustrates lithium secondary battery according to the exemplary embodiment of the disclosure.
As shown in Figure 1, in general, lithium secondary battery includes anode, cathode, diaphragm and electrolyte.Form electrode assembly The positive electrode, the negative electrode and the separator uses the component for being commonly used to manufacture lithium secondary battery.
Electrode may include electrode active material and binder according to the embodiment.More specifically, electricity according to the embodiment It extremely can be by being coated on electrode current collecting body through mixed electrode active material, binder, solvent and conductive material formation Then electrode slurry passes through dry and rolls electrode slurry and formed to predetermined thickness.Binder, which can be, to be described more fully below Binder for cathode.
Negative electrode active material for manufacturing cathode can be any negative electrode active material that can be embedded in and separate lithium ion Material.Negative electrode active material can be selected from include can reversibly absorb with the material of separating Li, alloy can be formed with lithium Any one or two or more combination in the group of metal material and its mixture.It can reversibly absorb and separate The material of lithium can be selected from including artificial graphite, natural graphite, graphitized carbon fibre, graphitized intermediate-phase carbosphere, fowler At least one of the group of alkene and amorphous carbon material.Amorphous carbon can be hard carbon, coke, 1500 DEG C or less roast MCMB and MPCF etc..Can with lithium formed alloy metal material can be selected from including Al, Si, Sn, Pb, Zn, Bi, In, Mg, At least one of group of Ga, Cd, Ni, Ti, Mn and Ge metal.Metal material can be used alone, or can be used in mixed way, Or can be formed alloy come using.Metal material may be used as the compound mixed with carbon-based material.
Negative electrode active material can be the compound of graphite base negative electrode active material and silicon (Si) base negative electrode active material.Though Right Si base negative electrode active material has high capacity, but Si base negative electrode active material may exceedingly be expanded in charge or discharge, To influence the adhesion strength of binder, life characteristic is caused to reduce.It is asked however, binder according to the embodiment can solve this Topic, to provide lithium ion battery excellent in terms of output characteristics, life characteristic and electrode adhesion stability.
Si base negative electrode active material includes silica, silicon particle, silicon alloy particle etc..The representative example of alloy include with Element silicon forms the solid solution of the aluminium (Al) of alloy, manganese (Mn), iron (Fe), titanium (Ti) etc., intermetallic compound, eutectic alloy Deng, but not limited to this.
Positive electrode active materials according to the embodiment for manufacturing anode may include allowing the reversible insertion of lithium and deintercalation Compound.More specifically, positive electrode active materials can be the combined oxidation of lithium with the metal in cobalt, manganese, nickel and combinations thereof At least one of object.
In addition to above-mentioned electrode active material and binder, electrode according to the embodiment can further include other additions Agent, such as decentralized medium, conductive material, viscosity modifier and packing material.
Diaphragm can prevent the short circuit between positive electrode and negative electrode, and provide the movable passageway of lithium ion.Diaphragm can be Polyolefin based polymer film or its multilayer film commonly known in the art, including it is polypropylene, polyethylene, polyethylene/polypropylene, poly- Ethylene/polypropylene/polyethylene and polypropylene, polyethylene/polypropylene and microporous membrane, fabric and non-woven fabrics fabric.It can make There is the porosity polyolefin film of the resin of high stability with coating.If electrolyte is the solid electrolyte of such as polymer, Then the solid electrolyte can also serve as diaphragm.
Electrolyte may include lithium salts and Non-aqueous Organic Solvents, and can further include and charge/put for improving Electrical characteristics and the additive for preventing overcharge.For example, lithium salts can be selected from including LiPF6、LiBF4、LiClO4、LiCl、 LiBr、LiI、LiB10Cl10、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、LiN (SO2C2F5)2、Li(CF3SO2)2N、LiC4F9SO3、LiB(C6H5)4、Li(SO2F)2N (LiFSI) and (CF3SO2)2In the group of NLi One or more materials mixture.
Non-aqueous Organic Solvents can be carbonic ester, ester, ether or ketone, can be used alone or is used in mixed way.Carbonic ester can To be dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), carbonic acid second third Ester (EPC), methyl ethyl carbonate (EMC), ethylene carbonate (EC), propene carbonate (PC), butylene (BC), fluoro carbonic acid Vinyl acetate (FEC), vinylene carbonate (VC) etc., ester can be gamma-butyrolacton (GBL), n- methyl acetate, n- ethyl acetate, N- propyl acetate etc., ether can be butyl oxide etc., but not limited to this.
Non-aqueous Organic Solvents can further include aromatic hydrocarbons organic solvent.The example of aromatic hydrocarbons organic solvent can be Benzene, fluorobenzene, bromobenzene, chlorobenzene, cyclohexylbenzene, cumene, n- butyl benzene, octyl benzene,toluene,xylene, mesitylene etc., and And it may be used alone or in combination.
Hereinafter, it will be described in detail the cathode of lithium secondary battery according to the embodiment.In the following description, unless It illustrates, otherwise unit is weight % (wt%).
The partial size of silica-base material according to embodiment as negative electrode active material greatly and can be less than for 50nm or more 10μm.The amount for the binder that cathode includes can be 1-50wt%, more preferably 5-30wt%.Conductive material and binder can To be included in cathode with the ratio of 1:1 to 1:10.
Silica-base material as electrode active material is as described above.Carbon black or gas-phase growth of carbon fibre (VGCF) may be used as Conductive material.
Accoding to exemplary embodiment, heparin, dopamine polymerization heparin and LiPAA (Lithium polyacrylate) may be used as bonding Agent.
Lithium secondary battery accoding to exemplary embodiment may include the compound of graphite and silicon as cathode.Further Ground, lithium secondary battery accoding to exemplary embodiment may include binder, in the binder, use in graphite-based cathode Such as carboxymethyl cellulose (CMC)/butadiene-styrene rubber (SBR) water based adhesive polymerize with such as heparin, dopamine heparin and The polymeric binder of LiPAA mixes, to increase the adhesion strength of silicon-based anode and inhibit the volume expansion of silicon-based anode, thus Improve the adhesiveness of the cathode of the compound including graphite and silicon.
Lithium secondary battery accoding to exemplary embodiment may include material of the energy density silicon higher than graphite as cathode Material, to increase energy density.However, silicon has the problem of volume expansion during charge or discharge.When charging reaches Li4.4When Si, to about 4 times, this leads to the separation and rupture of electrode for the volume expansion of silicon, so as to the stability to electrode with And the service life of electrode constitutes a threat to.Therefore, as described above, lithium secondary battery accoding to exemplary embodiment by include heparin, Dopamine polymerization heparin and LiPAA and CMC/SBR inhibit the volume expansion of silicon as binder and including graphite and silicon Compound is as cathode.
Heparin includes allowing hydrogen in conjunction with CMC or covalently bound multiple sites (site), can be used as crosslinking agent.Moreover, Functional group SO3 -Have the advantages that can contribute to transfer lithium ions.Moreover, because the catechol functional group of dopamine have with The strong adhesion strength of silicon materials, therefore adhesion strength can be physically improved by the way that dopamine to polymerize with heparin.In addition, LiPAA Li+The lithium ion conductive between silicon and conductive material can be improved in functional group.
In the following, it is described that the manufacturing method of the electrode of lithium secondary battery accoding to exemplary embodiment, including silicon, bonding The preparation method of the compound of agent and conductive material.
<first embodiment>
In the first embodiment, in order to prepare silicon, binder and the compound of conductive material, it will be dispersed in the oxygen in ethyl alcohol SiClx and LiPAA are put into ball-milling device, and the ZrO that will be mixed with the ratio of 20:12The mixture of ball and powder is put into ball In mill apparatus.When silica and binder and ball to be put into togerther in ball-milling device, ball-milling device is repeated 3 times following procedure: It is ground 1 hour, is rested 30 minutes with the speed of 500rpm.When the first process of lapping being repeated 3 times is completed, carbon is further added Black and the second process of lapping of progress.Second process of lapping can also be carried out in a manner of identical with the first process of lapping.It will pass through The composite powder of the silicon, binder and the conductive material that obtain after second process of lapping is heat-treated 1 at 300 DEG C in argon (Ar) gas Hour, obtain final powder.
<second embodiment>
In a second embodiment, cathode is prepared using the final powder synthesized according to first embodiment.Cathode is prepared, is made The ratio for obtaining electrode active material, conductive material and binder is 94:3:3, and makes stone in the electrode active material provided The ratio of ink and silica is 91.5:8.5.When conductive material includes gas-phase growth of carbon fibre, conductive material can be with 1:1's Ratio includes gas-phase growth of carbon fibre and carbon black.When conductive material does not include gas-phase growth of carbon fibre, conductive material can be only Including carbon black.Binder can include CMC and SBR with the ratio of 1:1.With the electrode active material of aforementioned proportion offer, conduction Material and binder can be dispersed in distilled water and be prepared into electrode slurry.Electrode slurry can be coated to the copper as collector Foil.Collector is dried after electrode slurry is coated to collector, the cathode for lithium secondary battery can be obtained.
Fig. 2 shows cathode accoding to exemplary embodiment.Fig. 3 A and Fig. 3 B are conceptually illustrated accoding to exemplary embodiment The charge/discharge of cathode changes.
As shown in fig. 2 and fig. 3 a, conventional silicon-graphite composite negative pole binder is uniformly distributed.Ordinary graphite cathode exists Volume expansion is little during charging and discharging, so that there is no problem the ratio of binder and conductive material is lower.However, Due to the volume expansion and low conductivity during charging and discharging, silicon-based anode need binder and conductive material have compared with High ratio.
Conductive material and binder are collected at big body by cathode accoding to exemplary embodiment by mechanical milling process On the silica-base material of product variation, to using same amount of binder, improve electrode compared with conventional anode Service life.As shown in fig. 2 and fig. 3b, binder is collected on silica-base material.
Referring to Fig. 3 A, the silica-base material of conventional anode is had the following problems: due to electric during charging process and discharge process Son transfer disconnects, and the silica-base material of conventional anode is likely to become dead particle (the c) (dead that cannot express capacity particle).However, cathode accoding to exemplary embodiment is by the way that binder to be collected at around silica-base material referring to Fig. 3 B Solves the above problem.
Fig. 4 shows the cycle performance figure of cathode accoding to exemplary embodiment.Fig. 5 shows accoding to exemplary embodiment negative The discharge cycle performance of pole.
As shown in figure 4, including gas-phase growth of carbon fibre in the cathode with ratio according to the second embodiment as conductive The cathode (BM w VGCF) of material and cathode (BM w Super-P) including carbon black as conductive material, and according to other systems The cathode for making condition manufacture, which is compared, has more stable performance.
Fig. 5 shows discharge cycle performance of the cathode when C multiplying power of discharging is 0.5C to 20C.As shown in figure 5, having basis In the cathode of the ratio of second embodiment include gas-phase growth of carbon fibre as conductive material cathode (BM w VGCF) and including Cathode (BMw Super-P) of the carbon black as conductive material has more excellent compared with the cathode manufactured according to other manufacturing conditions Good high rate performance and stability.
Therefore, binder according to the embodiment can provide excellent output characteristics, life characteristic and electrode adherency and stablize Property.
Binder according to the embodiment can inhibit the volume expansion of silicon in the combination electrode of graphite and silicon.
The ionic conductivity of lithium ion can be improved in binder according to the embodiment.
While there have been illustrated and described what some embodiments of the present disclosure, but it will be appreciated by those skilled in the art that not It in the case where the principle and essence that are detached from the disclosure, can be changed, the scope of the present disclosure is in claims and its is equal It is limited in scheme.

Claims (11)

1. a kind of lithium secondary battery, comprising:
Anode；
Cathode；
Diaphragm, setting is between the anode and the cathode；And
Electrolyte,
Wherein the cathode includes electrode active material, binder and conductive material comprising silica-base material and graphite, and
The binder includes any one of heparin and Lithium polyacrylate i.e. LiPAA.
2. lithium secondary battery according to claim 1, wherein the partial size of the silica-base material is big for 50nm or more and is less than 10μm。
3. lithium secondary battery according to claim 1, wherein the total weight based on the electrode active material, the cathode Including the amount of binder be 1 weight % or bigger and less than 50 weight %.
4. lithium secondary battery according to claim 1, wherein the conductive material includes carbon black and gas-phase growth of carbon fibre That is at least one of VGCF.
5. lithium secondary battery according to claim 1, wherein the cathode includes the conduction with the ratio of 1:1 to 1:10 Material and the binder.
6. lithium secondary battery according to claim 1, wherein the binder further comprises dopamine polymerization heparin.
7. a kind of manufacturing method of lithium secondary battery, comprising the following steps:
The first grinding is carried out to the electrode active material and binder that include silica-base material using ball-milling device；
Conductive material is added to the first of the electrode active material and the binder that obtain by first grinding Compound, and answered using the ball-milling device the second of the electrode active material, the binder and the conductive material It closes object and carries out the second grinding；And
To described the of the electrode active material, the binder and the conductive material that are obtained by second grinding Two compounds are heat-treated.
8. according to the method described in claim 7, the step of wherein carrying out the described first grinding includes:
The electrode active material and the binder are put into the ball-milling device；
In terms of weight %, the ZrO that will be mixed with the ratio of 20:12The compound of ball and powder is put into the ball-milling device；And
It is repeated 3 times following procedure: grinding 1 hour being carried out with the speed of 500rpm, is rested 30 minutes.
9. according to the method described in claim 7, the step of wherein carrying out the heat treatment includes:
Heat treatment 1 hour is carried out at 300 DEG C in argon gas, that is, Ar gas.
10. according to the method described in claim 7, wherein the conductive material includes carbon black and gas-phase growth of carbon fibre i.e. VGCF At least one of.
11. according to the method described in claim 7, wherein the binder includes heparin, Lithium polyacrylate i.e. LiPAA and more Any one of bar amine polymerization heparin.
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